Process of wet and dry wrinkleproofing cellulose fabric with an aminoplast resin and zinc chloride



United States Patent success or war rush pier wnmrrrnrnoorme ELLULOE FABRIC WliTH AN AMHNUPLASTI RESIN AND ZlNC CHLGRIDE Philip B. Roth, Somerviile, and Leonard Brooks Hallows, New Brunswick, N.ll., assignors to American Cyanamrd Company, New York, N.Y., a corporation of Maine No Drawing. Filed Nov. 16, 195 Ser. No. 852,975

2 Claims. (Cl. 8--l16.3)

The present invention relates to a process for treating textile materials, to compositions used in the treating of textile materials and the materials so treated.

More particularly, the present invention relates to a process for finishing cellulose containing materials to impart wet and dry wrinkle recovery thereto and to the textile material so finished.

With the advent of Wash 11 wear fabrics on the market, a need has developed for improved finishes that impart wrinkle resistance to cellulose containing materials while both in the wet and the dry state. The wash n wear finish should impart wrinkle recovery in the Wet state to enable the creases to move out of position during the evaporation of moisture or drying of the fabric, and in the dry state, such fabric should be resistant to wrinkling of the type normally produced as for example from the wearing of a given garment.

It is an object of the present invention to provide a process whereby wet and dry wrinkle recovery may be imparted to cellulose containing textile materials, which process is readily adaptable to most commercial finishing equipment.

it is a further object of the present invention to provide a process whereby the properties of wet and dry wrinkle recovery may be varied within certain limits with the result that characteristics of the final fabric may be readily custom designed.

It is a further object of the present invention to provide cellulose containing textile materials characterized by both wet and dry Wrinkle recovery of a high order.

These and other objects and advantages of the present invention will become more apparent from the detailed description set forth hercinbelow.

In accordance with the present invention, a process is provided for treating cellulosic textile materials which comprises applying thereto a Water-soluble aminoplast resin and a swelling agent for the cellulosic textile material. The said swelling agent should be employed in amounts of from between about and about 50% of the volume of the zinc chloride-water treating bath composition without the aminoplast resin. Thereafter the treated cellulose containing textile material is dried and the aminoplast resin cured thereon at a temperature of less than 350 F. in order to achieve good wet and ry wrinkle recovery with minimum reduction in tensile strength.

The water soluble aminoplast resin is applied to the textile material in amounts of from between 2% and about 15% based on the dry weight of the textile material and preferably in amounts of from between 3 and about 12% based on the dry weight of the textile material.

By the expression between about 5% and about 50% of the volume of the Zinc chloride-water treating bath without the aminoplast resin and similar expressions as they are employed herein, it is meant a solution that results from introducing between about 5 and 50 parts by weight of said swelling agent into a given container and thereafter adding sufiicient water to make up 100 parts by volume, where the parts by volume are to the parts by weight, as 1 milliliter of water is to 1 gram of water.

3,l8l,927 Patented May 4, 1%65 By the expression cellulose containing textile material as that term is employed herein, it is meant formed textile fabrics, whether they be knitted, woven, non- Woven, felted or otherwise formed, containing at least 50% of cellulosic fiber. The cellulosic fiber or formed fabric may be cotton, jute, hemp, viscose rayon, linen and the like, but is preferably cotton.

By the expression aminoplast resin as that term is employed herein, it is meant any of the better known textile finishing resins classifiable as amino resins of which include melamine formaldehyde condensates, guanamine formaldehyde condensates, triazone formaldehyde condensates, urea formaldehyde condensates, thiourea formaldehyde condensates, cyclic urea formaldehyde condensates, as for example, 1,2 propylene urea formaldehyde condensates, 1,3 propylene urea formaldehyde condensates, and their corresponding thiourea derivatives and the alkylated, such as methylated, ethylated, and the like, condensates of these aminoplast formaldehyde materials.

As examples of the melamine formaldehyde resins contemplated for use in the present invention, the following are illustrative: tris(methoxymethyl) melamine, trimmethoxymethyl) dimethylol melamine, hexakis (methoxymethyl) melamine, bis(methoxymethyl) methylol melamine and the like. Examples of suitable guanamine formaldehyde condensates include the formaldehyde and alkylated formaldehyde condensates of inethoxyacetoguanamine, propoxyacetoguanamine, butoxyacetoguanamine, lactoguanamine and others of the type known in the prior art and particularly those described in U.S. Patent 2,887,409. As examples of urea and cyclic urea formaldehyde resins contemplated by the present invention, the following are illustrative: dimethylol urea, methylated methylol urea, methylated methylol thiourea, dimethylol 1,2-propylene urea, dimethylol ethylene urea, dimethylol ethylene thiourea, dimethylol 1,3-propylene urea, methylated dimethylol 1,3-propylene urea, and the like.

Examples of triazone formaldehyde resins include dimethylol tetrahydro-5-ethyl-s-triazone-Z, dimethylol tetrahydro-S-(Z-hydroxyethyl)-s-triazone-2 and tetramethylol ethylene-5,5'-bis (tetrahydro-s-triazone-Z).

Of all of the exemplary aminoplast resins set forth above, the cyclic ureas, as for example, the dimethylol ethylene urea, dimethylol 1,2-propylene urea, dimethylol 1,3-propylene urea, are greatly preferred as will be evident from the samples appearing hereinbelow. It will be apparent that the illustrated resins set forth above may be employed singly or in combination with each other.

The swelling agent employed in the process of the present invention must be one which will swell cellulosic fibers and, preferably, one which in addition is capable of functioning as an accelerator for the aminoplast resin during its cure on the fabric. In addition, the swelling agent, if not characterized as being an accelerator for aminoplast resins, should not interfere with the action of accelerators employed in the process.

Of the swelling agents known, zinc chloride is greatly preferred in that it functions as a swelling agent for the cellulosic fibers present in the textile material and as a curing accelerator for the aminoplast resin employed. Additional swelling agents include zinc perchlorate, sodium thiocyanate, lithium bromate. While these latter swilling agents are highly effective, for the most part they are not suitable accelerators or catalysts for the amino plast resin and additional catalytic material must be added in order to effect the proper cure of the aminoplast resin. In such an instance, zinc chloride may be added, whereby additional swelling and catalytic function is simultaneous- 1y imparted, or one of the other better known textile finishing accelerators or catalysts may be employed. As examples of this latter group, metal salts, such as magnesium chloride, alumium chloride, zinc nitrate, ammonium sulfate, and the like, amine hydrochloride salts such as triethylamine hydrochloride or alkanolamine salts such as triethanolamine hydrochloride, and free acids such as oxolic acid, tartaric acid and the like.

The swelling agent is employed in the present process in amounts of up to 50% of a total zinc chloride-water treating bath composition without the aminoplast resin and preferably is within a range of about 5 and 35% by weight thereof. As will become more apparent hereinafter, amounts from between about -25% appear to produce the best over-all results with respect to wet and dry wrinkle recovery and tensil strength.

The effects obtained when applying thermosetting resins in conjunction with zinc chloride are thought to be due to the following properties of the zinc chloride:

(1) Its action as an accelerator of the thermosetting resins. (2) Its ability to swell the celluluose fibers.

Under the preferred conditions of this invention, approximately equal parts of resin and zinc chloride solids are employed or a slight excess of the zinc chloride is used.

In accordance with the present invention, the cellulose containing textile material may be finished by padding, spraying, immersing, dipping or otherwise treating or impregnating the textile material. Preferably, finishing is accomplished by padding in that this technique is more satisfactorily employed than the others mentioned in that it enables larger quantities of goods to be finished in comparatively short periods of time. The aminoplast resin and swelling agent may be applied to the cellulosic textile material separately or in a single application. If applied separately, the textile material is preferably treated by the aminoplast resin followed by the application before cure of the swelling agent and curing agent if required. Preferably, the swelling agent and aminoplast resin and accelerator, if required, are applied simultaneously from a pad bath to the goods to be finished. While it is possible to apply the swelling agent first, followed by the aminoplast resin, in general the results are not satisfactory.

It should in general be noted that many of the standard catalysts or accelerators employed by the textile finishing industry will to some extent impart both wet and dry wrinkle recovery, but it appears that in order to achieve high order values with respect to each of these properties, substantial amounts of accelerator are required. It has been our experience that this general requirement of large amounts of accelerator adversely affects tensile strength, color, general appearance, hand, drape or other qualities of the fabric to such an extent as to impair its saleability. Thus, for example, zinc nitrate will to some extent impart wet and dry wrinkle recovery to cellulose containing textile materials but at concentrations above 10% based on the weight of resin solids, goods so finished are markedly discolored. This is a material defect on white goods. Other acceleratiors as for example, magnesium chloride, one of the more widely used accelerators in the textile finishing industry, while capable of imparting to some degree wet and dry wrinkle recovery, is insufficiently active to produce acceptable wet and dry wrinkle recovery under low temperature curing conditions essential to the maintenance of acceptable tensile strength in the finished goods.

Thus, of all of the accelerators investigated, zinc chloride is characterized by the flexibility and functionality most suited for use in this invention. Principally, this is true in that Zinc chloride is a swelling agent for cellulosic fibers and in addition, is a highly active catalyst for aminoplast resins. This ability to swell cellulosic fibers and its high catalytic activity enables it to be employed on textile materials, which when subject to comparatively enema? dry wrinkle recovery and acceptable tensile strength.

For the most part, this result cannot be obtained with other accelerators at the same or higher temperatures. In accordance with the present invention, the time and temperature of cure should not exceed a minute and a half at 350 F. Even this curing temperature results in a comparatively low tensile strength, usually on the Order of about 42 lbs. and thus, preferably, the cure is effected for 2 minutes at about 225 F. to 1 minute at 300 F. In general, the higher the temperature of curing, the higher the wrinkle recovery in both the wet and the dry state and the lower the tensile strength. It further follows that the lower the temperature of curing, the lower the wet and dry wrinkle recovery values and the higher the tensile strength.

It should be noted that in cases Where a combination of swelling agent and curing agent for the aminoplast resin is employed, that the curing accelerator will be employed in amounts, based on the weight of resin solids, normally recommended for the given accelerator for the aminoplast resin. Usually for most known accelerators, this amounts to from between 1 and 25% based on the weight of resin solids. Thus, for example, in the case of magnesium chloride as an accelerator, it would be employed in amounts between 2% and 20% based on the weight of resin solids. In the case of alkanolamine hydrochlorides, the amount should be between 2% and 20% based on the weight of the resin solids.

It is postulated that at lower concentrations, the zinc chloride acts primarily as an accelerator, and produces good dry wrinkle recovery and slightly poorer wet wrinkle recovery, that is, it behaves similarly to many conventional curing accelerators such as magnesium chloride. At the higher concentrations, the zinc chloride acts as a swelling agent as well as an accelerator, and it is thought that the improvement in wet wrinkle recovery observed when resins are applied with higher concentrations of zinc chloride is due to the formation of relatively long crosslinks while the cellulose is in the swollen condition. As the cellulose shrinks during drying, progressively shorter crosslinks are formed. The final result is a series of crosslinks of different lengths. Most of the recovery of the Wet fabric may be due to the longer crosslinks, whereas the shorter crosslinks provide wrinkle recovery for the dry fabric.

At still higher concentrations of zinc chloride, where less dry wrinkle recovery is obtained while wet wrinkle recovery increases, it is believed that the majority of crosslinks formed While the cellulose is in a swollen condition. This may result from:

(1) Rapid and complete curing of the resin in the presence of high accelerator concentrations, while the fibers are still swollen.

(2) The restriction of the fiber shrinkage during drying by the high concentration of the zinc chloride present.

While the above illustrative theory is believed to be founded in merit, applicants do not wish to be restricted thereby since the exact reasons whereby the improved advantages of good wet and dry wrinkle recovery are not fully known.

In order that the present invention may be more fully understood, the following examples are given by way of illustration. No specific details or enumerations contained therein should be construed as limitations of the present invention except insofar as they appear in the appended claims. All parts and percents are by weight, unless specifically designated.

Wet and dry wrinkle recoveries reported hereinbelow were obtained as follows. The wrinkle recovery was measured on a Monsanto wrinkle recovery tester following the tentative test method No. 66-1956 described on page 158 of the 1957 Technical Manual and Yearbook of the American Association of Textile Chemists and Colorists, volume 33. The fabric was saturated with water before making the wet wrinkle recovery measure ment.

EXAMPLE 1 6% and 12% solids of dimethylol ethylene urea were applied to 80 x 80 cotton percale and to cotton poplin, with 7.5% and 15% resin solids, respectively in the bath, and with the following concentrations of zinc nitrate and zinc chloride:

(1) zinc nitrate on weight of resin solids.

(2) 17.6% zinc chloride on weight of resin solids (1.3%

and 2.6% zinc chloride in the bath).

(3) 12.5% zinc chloride in the bath.

(4) 25% zinc chloride in the bath.

The treated fabrics were dried and cured in one operation for 3 minutes at 300 F., process washed and evaluated for both wet and dry wrinkle recovery by the procedure described above. The results are given in Table I.

Table l 86 x 86 cotton Poplin Dry Wet Dry Wet wrinkle wrinkle wrinkle wrinkle recovery 1 recovery 1 recovery 1 recovery 1 Untreated 164 146 182 177 6% resin solids:

10% zinc nitrate (on 268 255 246 245 resin solids) 1.3% zinc chloride 268 241 247 250 12.5% zinc chloride.- 273 277 249 269 25% zinc chloride 253 282 239 275 12% resin solids:

10% zinc nitrate (on resin solids) 297 262 269 269 2.6% zinc chloride 281 253 264 264 12.5% zinc chloride 291 279 263 298 25% zinc chloride 264 290 252 298 1 Total in degrees. 2 17 .6% on resin solids in bath.

It will be noted from Table I that increasing the concentration of zinc chloride in the bath to 12.5% resulted in no significant change in the dry wrinkle recovery of percale or poplin treated with 6% or 12% resin solids. However, there was an increase in the wet wrinkle recovery of each fabric. For the poplin, the wet wrinkle recovery became greater than the dry, but for the percale,

the wet wrinkle recovery was improved to a level similar to that of the dry wrinkle recovery.

Increasing the concentration of zinc chloride in the bath to 25% resulted in further improvement in Wet wrinkle recovery, but there was a reduction in dry wrinkle recovery. At both 6% and 12% resin solids, and on both the percale and the poplin, the wet wrinkle recovery was considerably greater than the dry.

The fabrics with the higher wet wrinkle recoveries were resistant to wet creasing and showed some springiness.

EXAMPLE 2 5% solids of dimethylol ethylene urea, methylated dimethylol urea and methylated trimethylol melamine were applied to cotton percale, using the following accelerators and curing for 1.5 minutes at 350 F.:

(1) 5% zinc chloride in the pad bath. (2) zinc chloride in the pad bath. (3) zinc chloride in the pad bath.

The treated fabrics were evaluated for wet and dry wrinkle recovery by the procedure described above. Recovery from wet hand creasing and appearance after washing were also noted.

The results are shown in Table II.

Table II Wrinkle Appearance recovery after 3 washes 2 total, Wet hand degrees creasing recovery Tumble Drip dried dried Dry Wet Untreated. 153 180 1 1 1 Ethylene urea resin:

5% zinc chloride 263 262 4 4'5 4-5 15% zinc chloride 264 276 5 4-5 4-5 25% zinc chloride 256 295 5 4 4 Urea resin:

5% zinc chloride 252 249 4 4-5 4 15% zinc chloride 253 276 5 4-5 4 25% zinc chloride 228 293 5 4 4 Melamine resin:

5% zinc chloride 235 235 4 4-5 3-4 15% zinc chloride 235 260 5 4 4 25% zinc chloride 228 277 5 4 4 1 5Good spring and recovery 1No spring or recovery.

5Excellent appearance, completely free from wrinkles and creases; 1Badly wrinkled, creased and puckered.

The test results show that with increasing zinc chloride concentration there was marked increase in the wet wrinkle recovery. However, at the higher zinc chloride concentrations, the gain in wet wrinkle recovery was accompanied by a loss in dry wrinkle recovery.

The fabrics treated with the higher zinc chloride concentrations and having high wet wrinkle recoveries, had similar recovery from Wet hand creasing.

The best general results were obtained with dimethylol ethylene urea. Although the best wet wrinkle recovery was obtained with the higher zinc chloride concentrations, the best appearance after three Laundromat washes was given by the fabrics treated with the lower zinc chloride concentrations.

EXAMPLE 3 Applications of 6% and 12% solids of an approximately 1:1 molar blend of a highly methylated fully methylolated melamine and dimethylol ethylene urea were appied to x 80 cotton percale and cotton poplin by the procedure described in Example 1, substituting this resin blend for the resin of Example 1. The results are shown in Table III.

Table III 80 x 80 cotton Poplin Dry Wet Dry Wet wrinkle wrinkle wrinkle wrinkle recovery 1 recovery 1 recovery 1 recovery 1 Untreated 164 146 182 177 6% resin solids:

10% zinc nitrate (on resin solids) 274 234 249 245 1.3% zinc chloride 256 244 246 243 12.5% zinc chloride. 275 276 248 269 25% zinc chloride 264 293 251 288 12% resin solids: 10% zinc nitrate (on resin solids) 262 255 280 261 2.6% zinc chloride 2 278 246 266 258 12.5% zinc chloride 274 288 280 298 25% zinc chloride 246 299 257 302 1 Total in degrees. 2 17.6% on resin solids in bath.

The results obtained with the blend on the cotton poplin at both 6% and 12% resin solids were similar to those obtained with dimethylol ethylene urea. The results on the cotton percale were similar also, except that the wrinkle recovery was slightly lower when using zinc chloride as accelerator (17.6% on resin solids) than when using zinc nitrate.

EXAMPLE 4 '7 a cured under conditions ranging from 1 minute at 225 F. 'The treated fabrics were dried for 3 minutes at 225 F.

to 3 minutes at 300 F. The results are shown in Table Wet and dry wrinkle recoveries and tensile strength were then determined. The results are shown in Table VI.

Table IV Dried Cured Wrinkle recovery total, degrees 5% 21101, tensile strength 5% Z1101, Z1101, ZnCl, Time, Temp, Time, Tcmp., total, lb.

min. F. min. F.

Dry Wet Dry Wet Dry Wet With increasing zinc chloride concentrations, there was Table VI a decrease in the dry wrinkle recovery obtained.

With increasing time and temperature of cure, there was a decrease in tensile strength and an increase in both g g g v total, Tensile c al, wet and dry wrinkle recovery. g

ea t v 1 results Resin From Table IV 1t w1ll app r hat best 0 er al 5%Zn0h1 12% Mgclzz with respect to tens1le strength, wet and dry wrinkle rec ,1 c ,1

a I 0 covery are achieved at 2 minutes at 250 F. Dry Wet Dry wet EXAMPLE 5 Ethylene urea. 240 240 152 168 69 100 5% SOlldS of dimethylol ethylene urea and methylated Urea 211 213 150 157 22 112 dimethylol urea were applied to cotton percale, using the gigf l 222 214 144 142 78 m following accelerators and curing for 1.5 minutes at Melamine 180 196 156 13a 92 103 6 F Melamine-ethyl- 40 ene urea 219 221 159 170 81 103 (l) 12% magnesium chloride on the Weight of resin solids, (2) 5% zinc chloride in the pad bath.

The results are shown in Table V.

1 5-Good spring and recovery; 1No sprin or recovery.

-5-Exccllent appearance, completely free rom wrinkles and creases; 1Badly wrinkled, creased and puckered,

Fabrics treated with zinc chloride had a better appearance than the fabrics treated with magnesium chloride as the accelerator.

EXAMPLE 6 5% solids of dimethylol ethylene urea, methylated dimethylol urea, dimethylol urea, methylated trimethylol melamine and a 1:1 molar blend of a highly methylated fully methylolated melamine and dimethylol ethylene urea were applied to cotton percale, using as accelerators:

(1) 12% magnesium chloride on the weight of resin solids. (2) 5% Zinc chloride in the bath.

1 In the pad bath. 2 Based on resin solids.

These results show that for all the resins with low temperature curing, better wrinkle recoveries were obtained with the applications using zinc chloride than with the applications using magnesium chloride. Furthermore wet wrinkle recovery was equally as good as dry.

While the present invention has been described primarily in connection with the swelling agent, the accelerator and the aminoplast resin, it should be noted that suitable compositions, as for example, pad bath compositions, may contain in addition to these materials other textile finishing agents and assistants, as for example, lubricants, softeners, dicyandiamide, and the like.

We claim:

1. An aminoplast crease-proofing process for treating cellulose textile fabrics, at least 50% of the fibers of which are selected from the group consisting of cotton and viscose rayon, which consists in applying to said fabrics a single aqueous solution containing a water-soluble aminoplast textile crease-proofing resin and also containing from about 10% to about 50% by weight of zinc chloride, based on the volume of the aqueous solution Without the aminoplast resin, said application being such as to impart from 2% to about 15% of said water-soluble aminoplast resin to the cellulose textile fabric based on its dry weight, and thereafter heating the fabric containing the aminoplast resin at a temperature and for a time period sufficient to cure said resin and within the range of from about 225 F. for about 2 minutes to a minute and a half at 350 F. after the fabric has been dried to impart a high order of wet and dry wrinkle recovery.

2. An aminoplast crease-proofing process for treating cellulose textile fabrics, at least 50% of the fibers of which are selected from the group consisting of cotton and viscose rayon, which consists in applying to said fabrics a single aqueous solution containing a Water-soluble textile crease-proofing resin consisting essentially of dirnethylol ethylene urea and also containing from about 10% to about 25% by weight of zinc chloride, based on the volume of the aqueous solution without the resin, said application being such as to impart from 2% to about 15% of said water-soluble dimethylol ethylene urea to the cellulose textile fabric based on its dry weight, and thereafter drying the fabrics and curing the resin thereon at curing times and temperatures within the range of from about 225 F. for about 2 minutes to about 350 F. for about a minute and one-half to impart a high order of wet and dry wrinkle recovery thereto.

References Cited by the Examiner UNITED STATES PATENTS OTHER REFERENCES Cooke: Textile Research Journal, February 1957, pages [5 0-165.

Textile Research Journal, March 1961, pages 197-l99.

NORMAN G. TORCHIN, Primary Examiner.

MORRIS O. WOLK, ABRAHAM H. WINKELSTEIN,

Examiners. 

1. AN AMINOPLAST CREASE-PROOFING PROCESS FOR TREATING CELLULOSE TEXTILE FABRICS, AT LEAST 50% OF THE FIBERS OF WHICH ARE SELECTED FROM THE GROUP CONSISTING OF COTTON AND VISCOSE RAYON, WHICH CONSISTS IN APPLYING TO SAID FABRICS A SINGLE AQUEOUS SOLUTION CONTAINING A WATER-SOLUBLE AMINOPLAST TEXTILE CREASE-PROOFING RESIN AND ALSO CONTAINING FROM ABOUT 10% TO ABOUT 50% BY WEIGHT OF ZINC CHLORIDE, BASED ON THE VOLUME OF THE AQUEOUS SOLUTION WITHOUT THE AMINOPLAST RESIN, AND APPLICATION BEING SUCH AS TO IMPART FROM 2% TO ABOUT 15% OF SAID WATER-SOLUBLE AMINOPLAST RESIN TO THE CELLULOSE TEXTILE FABRIC BASED ON ITS DRY WEIGHT, AND THEREAFTER HEATING THE FABRIC CONTAINING THE AMINOPLAST RESIN AT A TEMPERATURE AND FOR A TIME PERIOD SUFFICIENT TO CURE SAID RESIN AND WITHIN THE RANGE OF FROM ABOUT 225;. FOR ABOUT 2 MINUTES TO A MINUTE AND A HALF AT 350*F. AFTER THE FABRIC HAS BEEN DRIED TO IMPART A HIGH ORDER OF WET AND DRY WRINKLE RECOVERY. 